Liquid crystal compositions

ABSTRACT

This invention relates to a liquid crystal composition and articles comprising the composition. The composition comprises at least one compound of each of the Formulas (I), (II) and (III), 
     
       
         
         
             
             
         
       
     
     as defined herein. A process for making the composition is also provided.

TECHNICAL FIELD

This invention relates to liquid crystal compositions that containmixtures of functionalized and non-functionalized compounds, toprocesses for preparing the liquid crystal compositions. and to articlesfabricated from the compositions,

BACKGROUND

Thermotropic liquid crystals are generally crystalline compounds withsignificant anisotropy in shape. That is, at the molecular level, theyare characterized by a rod-like or disc like structure. When heated theytypically melt in a stepwise manner, exhibiting one or more thermaltransitions from a crystal to a final isotropic phase. The intermediatephases, known as mesophases, can include several types of smectic phaseswherein the molecules are generally confined to layers; and a nematicphase wherein the molecules are aligned parallel to one another with nolong range positional order. The liquid crystal phase can be achieved ina heating cycle, or can be arrived at in cooling from an isotropicphase. The structure of liquid crystals in general, and twisted nematicliquid crystals in particular, is further discussed in “The Physics ofLiquid Crystals”, de Gennes and Prost, Oxford University Press, 1995.

An important variant of the nematic phase is one wherein a chiral moietyis present, referred to as a twisted nematic or cholesteric phase. Inthis case, the molecules are parallel to each other as in the nematicphase, but the director of molecules (the average direction of therodlike molecules) changes direction through the thickness of a layer toprovide a helical packing of the nematic molecules. The pitch of thehelix is perpendicular to the long axes of the molecules. This helicalpacking of anisotropic molecules leads to important and characteristicoptical properties of twisted nematic phases including circulardichroism, a high degree of rotary power; and the selective reflectionof light, including ultraviolet, visible, and near-IR light. Reflectionin the visible region leads to brilliantly colored layers. The sense ofthe helix can either be right-handed or left-handed, and the rotationalsense is an important characteristic of the material. The chiral moietyeither may be present in the liquid crystalline molecule itself, forinstance, as in a cholesteryl ester, or can be added to the nematicphase as a dopant, with induction of the cholesteric phase. Thisphenomenon is further discussed in sources such as Bassler and Labes, J.Chem. Phys., 52, 631 (1970).

There has been interest in preparing stable polymer layers exhibitingnematic and/or cholesteric optical properties. One approach has been tosynthesize monofunctional and/or polyfunctional reactive monomers thatexhibit a nematic or cholesteric phase upon melting, formulate a lowmelting liquid crystal composition, and polymerize the liquid crystalcomposition in its nematic or cholesteric phase to provide a polymernetwork exhibiting stable optical properties of the nematic orcholesteric phase. Use of cholesteric monomers alone, as disclosed inU.S. Pat. No. 4,637,896 for example, provides cholesteric layers withthe desired optical properties, but the polymer layers possessrelatively weak mechanical properties.

A need thus remains for liquid crystal compositions that have broadthermal windows, low melting points and good phase stability againstcrystallization, and that are easy to prepare and can be tuned to givedesired properties.

SUMMARY

One embodiment of the inventions hereof provides a composition thatcontains at least one compound of the group of compounds represented bythe structures of each of the following Formulas (I), (II) and (III),

wherein

Z is F, Cl, Br, I, —OTs, —OTf, —OMs, CN, or NO₂;

Y is H, F, Cl, Br, I, —OTs, —OTf, —OMs, CN, or NO₂;

with the proviso that Z is not equal to Y;

-   n1, n2, n3, n4, n5, and n6 are each independently integers 3 to 20;-   m and p are each independently integers 0, 1, or 2;-   A is a divalent radical selected from the group:

wherein R³ through R¹⁰ are each independently selected from the group:H, C₁ to C₈ straight or branched chain alkyl, C₁ to C₈ straight orbranched chain alkyloxy, F, Cl, phenyl, —C(O)CH₃, CN, and CF₃; X² is adivalent radical selected from the group: —O—, —(CH₃)₂C—, and —(CF₃)₂C—;and each B¹ and B² is a divalent radical independently selected from thegroup: R¹¹-substituted-1,4-phenyl, wherein R¹¹ is H, —CH₃ or —OCH₃;2,6-naphthyl; and 4,4′-biphenyl; with the proviso that when m+p is equalto 3 or 4, at least two of B¹ and B² are R¹¹-substituted-1,4-phenyl.

Another embodiment of the invention is a liquid crystal compositioncomprising at least one compound of each of the Formulas (I), (II), and(III), and in a further embodiment the liquid crystal compositioncomprises at least one chiral compound.

Another embodiment of the invention is an article comprising the liquidcrystal composition, and in a further embodiment the article isfabricated as an optical element.

Another embodiment of the inventions hereof is a process for preparing acomposition by

(a) providing one or more organic polyol(s) comprising at least twohydroxyl groups and at least two covalently bonded carbon atoms, eachhydroxyl group being bonded to a different carbon atom within an organicpolyol;

(b) reacting the organic polyol(s), optionally in the presence of abase, with (i) one or more functionalized alkyl acid(s) or acidhalide(s) represented by the structure of the following Formula (X):

Z-(CH₂)_(n)—C(O)X   (X)

wherein X is Cl, Br, I, or OH; Z is F, Cl, Br, I, —OTs, —OTf, —OMs, CN,or NO₂;

-   and n is an integer equal to 3 to 20; and-   (ii) one or more non-functionalized alkyl acid(s) or acid halide(s)    represented by the structure of the following Formula (XI):

Y—(CH₂)_(t)—C(O)X   (XI)

wherein X is Cl, Br, I, or OH; Y is H, F, Cl, Br, I, —OTs, —OTf, —OMs,CN, or NO₂; and t is an integer equal to 3 to 20;

-   with the proviso that Z is not equal to Y; in a reaction solvent and    at a reaction temperature to provide a mixture comprising the    composition and a spent reaction mixture.

In another embodiment, the invention provides a composition as preparedby the process disclosed above; and in another embodiment, thecomposition prepared by the process disclosed above comprises at leastone compound of each of the Formulas (I), (II) and (III).

The composition as described herein has a variety of uses in liquidcrystal compositions. Choices may be made from within and among theprescribed ranges for the variable radicals and substituents such thateach compound of the composition is, for example, either symmetric orasymmetric.

DETAILED DESCRIPTION

One embodiment of the inventions hereof provides a compositioncomprising at least one compound of each of the Formulas (I), (II) and(III),

wherein

Z is F, Cl, Br, I, —OTs, —OTf, —OMs, CN, or NO₂;

Y is H, F, Cl, Br, I, —OTs, —OTf, —OMs, CN, or NO₂;

with the proviso that Z is not equal to Y;

n1, n2, n3, n4, n5, and n6 are each independently integers 3 to 20;

m and p are each independently integers 0, 1, or 2; and

A is a divalent radical selected from the group:

wherein R³ through R¹⁰ are each independently selected from the group:H, C₁ to C₈ straight or branched chain alkyl, C₁ to C₈ straight orbranched chain alkyloxy, F, Cl, phenyl, —C(O)CH₃, CN, and CF₃; X² is adivalent radical selected from the group: —O—, —(CH₃)₂C—, and —(CF₃)₂C—;and each B¹ and B² is a divalent radical independently selected from thegroup: R¹¹-substituted-1,4-phenyl, wherein R¹¹ is H, —CH₃ or —OCH₃;2,6-naphthyl; and 4,4′-biphenyl; with the proviso that when m+p is equalto 3 or 4, at least two of B¹ and B² are R¹¹-substituted-1,4-phenyl.

The abbreviation “—OTf”, as used herein, refers to a functional groupwith the formula CF₃SO₃—, which is also referred to as a triflate ortrifluoromethanesulfonate group. The abbreviation “—OTs”, as usedherein, refers to a functional group with the formula CH₃C₆H₄SO₃—, whichis also referred to as a tosylate group. The abbreviation “—OMs”, asused herein, refers to a functional group with the formula CH₃SO₃—,which is also referred to as a mesylate or methanesulfonate group.

In the phrase “each B¹ and B² is a divalent radical independentlyselected from the group . . . ”, when m=2, the two B¹ units are eachselected independently, that is they may be the same or different; andwhen p=2, the two B² units are each selected independently, that is theymay be the same or different. In addition, a C₁-C₈ group may be any oneor more of C₁, C₂, C₃, C₄, C₅, C₆, C₇ or C₈. Throughout thespecification, in Formulas (I), (II), (III), when -A- is atrans-cyclohexyl moiety and one or both of m and p is an integer equalto 0, the term “aryl alkanoate ester(s)” can refer to cyclohexylalkanoate ester(s).

For each compound of the composition, n1, n2, n3, n4, n5, and n6 mayeach be independently integers 3 to 10. For each compound of thecomposition, when m and p=2, B¹ and B² may each be independentlyR¹¹-substituted-1,4-phenyl.

In one embodiment, Z is Br, I, —OTs, —OTf, or —OMs, and Y is H, Br, I,—OTs, —OTf, or —OMs. In another embodiment, Z is Br and Y is H. Inanother embodiment, for at least one compound of each of the Formulas(I), (II), (III) of the composition, m is 0 and p is 0. In anotherembodiment, for at least one compound of each of the Formulas (I), (II),(III) of the composition, m is 1 and p is 0. In another embodiment, forat least one compound of each of the Formulas (I), (II), (III) of thecomposition, m is 1 and p is 1. In another embodiment, for at least onecompound of each of the Formulas (I), (II), (III) of the composition, mis 1 and p is 0, and for at least one compound of each of the Formulas(I), (II), (III) of the composition, m is 1 and p is 1. In anotherembodiment, n1, n2, and n4 are the same. In another embodiment, thecomposition comprises only one compound of Formula (I). In anotherembodiment, the composition comprises only one compound of Formula (I)and n1, n2, and n4 are the same.

Another embodiment of the invention is a composition comprising at leastone compound of each of the Formulas (I), (II), and (III), wherein forat least one compound of each of the Formulas (I), (II) and (III), m is0 and p is 0, and, Formula (I) is selected from the group compoundsrepresented by the structures of the following Formulas (VIIa-VIIf):

In this embodiment, Formula (II) is selected from the group of compoundsrepresented by the structures of the following Formulas (XVIIa-XVIIf):

and Formula (III) is selected from the group of compounds represented bythe structures of the following Formulas (XVIIIa-XVIIIf):

Compositions comprising at least one compound of each of the Formulas(VIIa-VIIf), (XVIIa-XVIIf), and (XVIIIa-XVIIIf) are useful as diluentsand viscosity modifiers for liquid crystal compositions. Methods forsynthesizing these compositions are described below. Preferredcompositions comprise at least one compound as described in Formulas(VIIa-VIId) wherein R³-R⁸ are H; in Formula (VIIa) wherein R³-R⁵ are Hand R⁶ is CH₃; and in Formula (VIIe) wherein X² is —C(CH₃)₂— or —O—.

Another embodiment of the invention is a composition comprising at leastone compound of each of the Formulas (I), (II) and (III), wherein for atleast one compound of each of the Formulas (I), (II) and (III), m is 1and p is 0, and Formula (I) is selected from the group of compoundsrepresented by the structures of the following Formulas (VIIIa-VIIIe):

In this embodiment, Formula (II) is selected from the group of compoundsrepresented by the structures of the following Formulas (XIXa-XIXe):

and Formula (III) is selected from the group of compounds represented bythe structures of the following Formulas (XXa-XXe):

Compositions comprising at least one compound of each of the Formulas(VIIIa-VIIIe), (XIXa-XIXe), and (XXa-XXe) are useful in liquid crystalcompositions. Such compositions, when comprising at least one compoundas described in Formula (VIIIa-VIIIe), exhibit nematic phases at or nearroom temperature (RT, about 25° C.). Other liquid crystal monomers canbe added to the composition to provide nematic phases over broadtemperature ranges. Other compounds within this group may exhibit lowmelting points and can be used as reactive diluents and viscositymodifiers in liquid crystal mixtures. Preferred compositions comprise atleast one compound as described in Formula (VIIIa) wherein R³-R⁶ is H.Methods for synthesizing these compositions are described below.

Another embodiment of the invention is a composition comprising at leastone compound of each of the Formulas (I), (II), and (III), wherein forat least one compound of each of the Formulas (I), (II), and (III), m is1 and p is 1, and Formula (I) is selected from the group of compoundsrepresented by the structures of the following Formulas (IXa-IXe):

In this embodiment, Formula (II) is selected from the group of compoundsrepresented by the structures of the following Formulas (XXIa-XXIe):

and Formula (III) is selected from the group of compounds represented bythe structures of the following Formulas (XXIIa-XXIIe):

Compositions comprising at least one compound of each of the Formulas(IXa-IXe), (XXIa-XXIe), and (XXIIa-XXIIe) are useful in liquid crystalcompositions. Such compositions, when comprising at least one compoundas described in Formula (IXa-IXe), exhibit nematic phases over broadtemperature ranges. Other liquid crystal monomers can be added to thecomposition to provide nematic phases over broad temperature ranges.Preferred compositions comprise at least one compound as described inFormula (IXa) wherein B¹ and B² are R¹¹-substituted-1,4-phenyl. Withinthis group of compositions, a more preferred composition furthercomprises at least one compound wherein one of the group R³-R⁶ is Cl orCH₃; and three of the group R³-R⁶ are H—as shown, for example, in thefollowing Formula (XXIII):

Within these preferred compositions, more preferred are those comprisingcompounds wherein n1 and n2 are, independently, integers 3 to 10.Methods for synthesizing these compositions are described below.

Another embodiment of the invention is a composition comprising at leastone compound of each of the Formulas (I), (II) and (III), wherein for atleast one compound of each of the Formulas (I), (II) and (III), m is 1and p is 0; and wherein for at least one compound of each of theFormulas (I), (II) and (III), m is 1 and p is 1. Such compositions canbe useful in liquid crystal compositions and can exhibit nematic phasesat or near room temperature (RT). Other liquid crystal monomers can beadded to the composition to provide nematic phases over broadtemperature ranges. Preferred compositions comprise at least onecompound as described in Formula (VIIIa) and/or Formula (IXa) whereinR³-R⁶ is H. Other preferred compositions comprise at least one compoundof Formula (XXIII). Other preferred compositions comprise at least onecompound as described in Formula (VIIIa) and/or Formula (IXa) whereinone of the groups R³-R⁶ is CH₃; and three of the groups R³-R⁶ are H.Methods for synthesizing these compositions are described below.

In another embodiment, the total amount of compounds of Formula (I) arepresent in the range of about 0.1 mole percent to about 95 mole percentbased on the total content of the composition. In another embodiment,the total amount of compounds of Formula (I) are present in the range ofabout 5 mole percent to about 95 mole percent based on the total contentof the composition. In another embodiment, the total amount of compoundsof each of Formula (I) are present in the range of about 20 mole percentto about 80 mole percent based on the total content of the composition.

In another embodiment, the total amount of compounds of Formula (II) arepresent in the range of about 5 mole percent to about 50 mole percent,based on the total content of the composition. In another embodiment,the total amount of compounds of Formula (II) are present in the rangeof about 10 mole percent to about 50 mole percent based on the totalcontent of the composition.

In another embodiment, the total amount of compounds of Formula (III)are present in the range of about 0.1 mole percent to about 90 molepercent based on the total content of the composition. In anotherembodiment, the total amount of compounds of Formula (III) are presentin the range of about 0.1 mole percent to about 60 mole percent based onthe total content of the composition.

When the compositions of this invention are prepared by one embodimentof a process hereof (such as is disclosed below), rather than bysynthesizing each compound individually and then combining them to formthe desired composition, one result of the use of that embodiment of theprocess is that the relative amounts of the compounds of each of theFormulas (I), (II) and (III) in the composition will be determined by afixed relationship that is given effect by the process. When thecomposition is prepared by that embodiment of a process hereof, adesired amount of the compounds of one of Formulas (I), (II) or (III) ispre-selected, and an appropriate ratio of the reactants is employed toproduce the desired amount of the compounds of that Formula. The ratioof reactants selected to produce the desired amount of one of theFormula (II), (II) or (III) compounds will, however, also produce anamount of the other two compounds that adheres to the fixedrelationship. For example, in this embodiment of the process, the amountof each of the Formula (I), (II) or (III) compounds that is produced inrelation to the amount of leaving groups used in the reactants willadhere to a fixed relationship that may be determined in advance.

The choice of what amount to pre-select for which of the compounds ofthe Formulas (I), (II) or (III) depends on the desired end use of thecomposition, for example the degree of flexibility or brittlenessdesired. The preparation by a process hereof of the compositions hereof,which comprise at least one compound of each of the Formulas (I), (II)and (III), can thus provide advantages over compositions comprising asingle compound, compositions comprising compounds of less than all ofthe Formulas (I), (II) and (III), or compositions prepared by blendingseparately made compounds because the physical properties of thecompositions hereof may thus be tuned by adjusting the relativepercentage content of each of the Formula (I), (II) and (III) compounds.For example, the rate of crystallization, the thermal characteristics,or the degree of crosslinking (and thus the flexibility or brittleness)of a composition hereof may be adjusted in such manner.

Another embodiment of the invention hereof provides a process forpreparing a composition which comprises at least one compound of each ofthe Formulas (I), (II) and (III). In one embodiment, the processcomprises

(a) providing one or more organic polyol(s) comprising at least twohydroxyl groups and at least two covalently bonded carbon atoms, eachhydroxyl group being bonded to a different carbon atom within an organicpolyol; and

(b) reacting the organic polyol(s), optionally in the presence of abase, with (i) one or more functionalized alkyl acid(s) or alkyl acidhalide(s) as represented by the structure of the following Formula (X):

Z-(CH₂)_(n)—C(O)X   (X)

wherein X is Cl, Br, I, or OH; Z is F, Cl, Br, I, —OTs, —OTf, —OMs, CN,or NO₂;

-   and n is an integer equal to 3 to 20; and-   (ii) one or more non-functionalized alkyl acid(s) or acid halide(s)    as represented by the structure of the following Formula (XI):

Y—(CH₂)_(t)—C(O)X   (XI)

wherein X is Cl, Br, I, or OH; Y is H, F, Cl, Br, I, —OTs, —OTf, —OMs,CN, or NO₂; and t is an integer equal to 3 to 20; with the proviso thatZ is not equal to Y; in a reaction solvent and at a reaction temperatureto provide a mixture comprising at least one compound of each of theFormulas (I), (II), and (III), as described above, and a spent reactionmixture. Preferably, when X is OH, the process further comprises the useof a carbodiimide dehydrating agent.

In various embodiments of the processes of the invention, the polyol(s)may be selected from the group of compounds represented by thestructures of the following Formulas (XIIa-XIIf):

wherein R³-R¹⁰ and X² are as described above. These embodiments of theprocess can be used to provide compositions comprising compounds ofFormula (VIIa-VIIf) as described above. Specific diols of Formula(XIIa-XIIf) useful and preferred in the process include: hydroquinone,methylhydroquinone, chlorohydroquinone, 4,4′-dihydroxybiphenyl,2,6-dihydroxynapthalene, 1,5-dihydroxynapthalene, Bisphenol A,6F-Bisphenol A, 4,4′-oxydiphenol, and trans-1,4-cyclohexanediol.

In other embodiments of the processes hereof, the polyol(s) may includeone or more ester diols selected from the group of compounds representedby the structures of the following Formulas (XIIIa-XIIIg):

wherein R³-R¹¹ are as described above. These embodiments of the processcan be used to provide compositions comprising compounds of Formulas(VIIIa-VIIIe) as described above. Specific ester diols of Formulas(XIIIa-XIIIg) useful and preferred in the process include:4-hydroxyphenyl 4-hydroxybenzoate, 2-methyl-4-hydroxyphenyl4-hydroxybenzoate, 3-methyl-4-hydroxyphenyl 4-hydroxybenzoate,2-chloro-4-hydroxyphenyl 4-hydroxybenzoate, 3-chloro-4-hydroxyphenyl4-hydroxybenzoate, 2-fluoro-4-hydroxyphenyl 4-hydroxybenzoate,3-fluoro-4-hydroxyphenyl 4-hydroxybenzoate, 2-phenyl-4-hydroxyphenyl4-hydroxybenzoate, 3-phenyl-4-hydroxyphenyl 4-hydroxybenzoate,6-hydroxynaphthyl 4-hydroxybenzoate, 5-hydroxynaphtyl 4-hydroxybenzoate,4-(4′-hydroxybiphenyl) 4-hydroxybenzoate, trans-4-hydroxycyclohexyl4-hydroxybenzoate, trans-4-hydroxycyclohexyl4-hydroxy-3-methoxybenzoate, 4-hydroxyphenyl4-hydroxy-3-methoxybenzoate, 2-methyl-4-hydroxyphenyl4-hydroxy-3-methoxybenzoate, 3-methyl-4-hydroxyphenyl4-hydroxy-3-methoxybenzoate, 2-chloro-4-hydroxyphenyl4-hydroxy-3-methoxybenzoate, 3-chloro-4-hydroxyphenyl4-hydroxy-3-methoxybenzoate, 4-hydroxyphenyl 4-hydroxy-3-methylbenzoate,2-methyl-4-hydroxyphenyl 4-hydroxy-3-methylbenzoate, and3-methyl-4-hydroxyphenyl 4-hydroxy-3-methylbenzoate.

Other ester diols useful and preferred in the processes that providecompositions comprising specific compounds as described by Formula(XIIIe) derived from 6-hydroxy-2-napthalene carboxylic acid are:6-hydroxynapthalene-2-carboxylic acid 4-hydroxyphenyl ester (CAS No.[17295-17-9]), 6-hydroxynapthalene-2-carboxylic acid2-methyl-4-hydroxyphenyl ester, 6-hydroxynapthalene-2-carboxylic acid3-methyl-4-hydroxyphenyl ester, 6-hydroxynapthalene-2-carboxylic acid2-chloro-4-hydroxyphenyl ester, and 6-hydroxynapthalene-2-carboxylicacid 3-chloro-4-hydroxyphenyl ester.

Other ester diols useful and preferred in the processes that providecompositions comprising specific compounds as described in Formula(XIIIg) derived from 4′-hydroxy-4-biphenyl carboxylic acid include:4′-hydroxybiphenyl-4-carboxylic acid 4-hydroxyphenyl ester,4′-hydroxybiphenyl-4-carboxylic acid 2-methyl-4-hydroxyphenyl ester,4′-hydroxybiphenyl-4-carboxylic acid 3-methyl-4-hydroxyphenyl ester,4′-hydroxybiphenyl-4-carboxylic acid 2-chloro-4-hydroxyphenyl ester, and4′-hydroxybiphenyl-4-carboxylic acid 3-chloro-4-hydroxyphenyl ester.

In other embodiments of the processes hereof, the polyol(s) may includeone or more diester diol(s) selected from the group of compoundsrepresented by the structures of the following Formulas (XIVa-XIVf):

wherein R³-R¹¹ are as described above. These embodiments of the processcan be used to provide compositions comprising compounds as described inFormula (IXa-IXe) described above. Specific diester diols of Formula(XIVa-XIVf) useful and preferred in the process include the compoundslisted in Table 1 that are specific examples of compounds of Formula(XIVa-XIVf).

TABLE 1 Examples of Diester Diols of Formula (XIVa-f)

Using a mixture of two or more polyols is one means to increase thecomplexity of the product distribution of the resulting composition.This can be a way to tune the properties of the composition or theproperties of its end use. The polyols can be selected to provide acomposition having two or more mesogens, for example a compositionwherein for at least one compound of each of the Formulas (I), (II) and(III) m is 1 and p is 0, and wherein for at least one compound of eachof the same Formulas m is 1 and p is 1. Other combinations of polyolscan also be used.

Preferred functionalized alkyl acid halide(s) as described in Formula(X) are acid chlorides (X═Cl). In one embodiment, in Formula (X) Z isBr, I, —OTs, —OTf, or —OMs. Preferred non-functionalized alkyl acidhalide(s) as described in Formula (XI) are acid chlorides (X═Cl). In oneembodiment, in Formula (XI) Y is H, Br, I, —OTs, —OTf, or —OMs. In oneembodiment, in Formula (X) Z is Br and in Formula (XI) Y is H.

When the organic polyol is a diol, the total amount of thefunctionalized alkyl acid halide(s) and the non-functionalized alkylacid halide(s) is preferably about 1.8 to about 2.5 equivalents, andmore preferably about 2.0 equivalents, based on the amount of the diol.The relative amounts of the functionalized and non-functionalized alkylacid halides used determine the relative amounts of the compounds ofFormulas (I), (II) and (III) obtained in the composition. For example, a1:1 mixture (on a mole basis) of a functionalized and anon-functionalized alkyl acid halide provides a composition wherein therelative molar amounts of the compounds of Formulas (I), (II) and (III)are 1:2:1, respectively. Alternatively, a 4:1 mixture (on a mole basis)of a functionalized and a non-functionalized alkyl acid halide (forexample, 1.6 equivalents of a functionalized and 0.4 equivalents of anon-functionalized alkyl acid halide, relative to the diol) results in acomposition having 64 mol % compounds of Formula (I), 32 mol % compoundsof Formula (II), and 4 mol % compounds of Formula (III). For aparticular ratio of functionalized to non-functionalized alkyl acidhalide(s), the distribution of products is a statistical mixture of allthe possibilities. Increasing the total number of functionalized and/ornon-functionalized alkyl acid halides is one means to increase thecomplexity of the product distribution, i.e. the number of compounds ofeach of Formulas (I), (II) and (III), of the resulting composition.

In another embodiment, the relative amounts of the functionalized andnon-functionalized alkyl acid halides are selected to provide acomposition comprising at least one compound of each of the Formulas(I), (II) and (III), wherein the total amount of compounds of Formula(I) are present in the range of about 0.1 mole percent to about 95 molepercent based on the total content of the composition. In anotherembodiment, the relative amounts of the functionalized andnon-functionalized alkyl acid halides are selected to provide acomposition wherein the total amount of compounds of Formula (I) arepresent in the range of about 5 mole percent to about 95 mole percentbased on the total content of the composition. In another embodiment,the relative amounts of the functionalized and non-functionalized alkylacid halides are selected to provide a composition wherein the totalamount of compounds of Formula (I) are present in the range of about 20to about 80 mole percent based on the total content of the composition.

In another embodiment, the relative amounts of the functionalized andnon-functionalized alkyl acid halides are selected to provide acomposition comprising at least one compound of each of the Formulas(I), (II) and (III), wherein the total amount of compounds of Formula(II) are present in the range of about 5 mole percent to about 50 molepercent based on the total content of the composition. In anotherembodiment, the relative amounts of the functionalized andnon-functionalized alkyl acid halides are selected to provide acomposition wherein the total amount of compounds of Formula (II) arepresent in the range of about 10 to about 50 mole percent based on thetotal content of the composition.

In another embodiment, the relative amounts of the functionalized andnon-functionalized alkyl acid halides are selected to provide acomposition comprising at least one compound of each of the Formulas(I), (II) and (III), wherein the total amount of compounds of Formula(III) are present in the range of about 0.1 mole percent to about 90mole percent based on the total content of the composition. In anotherembodiment, the relative amounts of the functionalized andnon-functionalized alkyl acid halides are selected to provide acomposition wherein the total amount of compounds of Formula (III) arepresent in the range of about 0.1 mole percent to about 60 mole percentbased on the total content of the composition.

This process, or derivations thereof using several functionalized alkylacid halides in conjunction with several non-functionalized alkyl acidhalides, is a convenient and preferred process to provide complexmixtures of the composition.

The reaction solvent can be any solvent known in the art to be useful inperforming acid halide condensations with alcohols, including alkylethers such as tetrahydrofuran (THF), dioxane or dimethoxyethane; alkylesters such as ethyl acetate or butyl acetate; hydrocarbons such asxylenes or toluene; halogenated hydrocarbons such as 1,2-dichloroethaneor dichloromethane; and amides such as dimethylformamide ordimethylacetamide (DMAc). A preferred reaction solvent is THF.

The reaction temperature is a temperature that gives a reasonable rateof reaction with a minimum of by-products. The reaction temperaturegenerally is between −30° C. and about 50° C., and preferably about 0°C. to about room temperature (RT, e.g. 25° C.).

A base, when optionally used in step (b), can include an inorganic base,for instance an alkali metal or alkali earth metal hydroxide, carbonateor bicarbonate; or an organic base such as an amine base that has atleast two aliphatic groups, or in which the N atom is in acycloaliphatic or aromatic ring, substituted in a manner that inducessteric crowding around the N atom. Typically the amine base will be oflow water solubility and have a pK_(a) of the conjugate acid of about10. Thus, it may be a heteroaromatic base such as pyridine or asubstituted pyridine, for example 2,6-dimethylpyridine; or it may be asecondary amine providing it is sufficiently sterically hindered. Anexample of a suitable secondary amine is 2,2,6,6-tetramethyl-piperidine.Preferably, however, it is a tertiary amine of formula R¹²R¹³R¹⁴Nwherein R¹², R¹³ and R¹⁴ are each independently C₁-C₁₀ alkyl groups orC₃-C₆ cycloalkyl groups. The alkyl groups may be straight or branchedchain. Examples of suitable alkyl groups include methyl, ethyl,isopropyl, n-propyl, n-butyl, sec-butyl and tert-butyl. Suitabletertiary amines of formula R¹²R¹³R¹⁴N are, for example,N,N-diisopropylethylamine, N,N-dimethylaniline, triethylamine,t-butyldimethylamine, N,N-diisopropylmethylamine,N,N-diisopropylisobutylamine, N,N-diisopropyl-2-ethylbutylamine,tri-n-butylamine. Preferred are amine bases selected from the group:triethylamine, diisopropylethylamine, tributyl amine, pyridine, and2,6-dimethylpyridine. The base is preferably present in an amount ofabout 0.8 to about 5 equivalents per equivalent of the total alkyl acidhalide(s) used, that is the sum of the functionalized and thenon-functionalized alkyl acid halides.

When the base optionally used in step (b) is an amine base, a by-productof the reaction is an amine salt such as an amine hydrochloride. In oneembodiment the amine salt is removed from the spent reaction mixture by,for instance, filtering the reaction mixture. In another embodiment, themixture comprising at least one compound of each of the Formulas (I),(II) and (III) provided by step (b) can be separated from the spentreaction mixture by a variety of methods known in the art. Preferredmethods include any one or more of the steps: filtering the amine saltby-product; precipitating the reaction mixture into water and filtering;partitioning the reaction mixture with water and/or organic solvents;washing with reaction mixture with water; drying the reaction mixturewith a drying agent; removal of solvent by evaporation; and washing thecrude product with one or more solvents which selectively removebyproducts without dissolving the mixture of compounds of Formulas (I),(II) and (III).

When used in step (b), a suitable carbodiimide dehydrating agent may beany diimide commonly used in coupling acids with alcohols and phenols. Apreferred carbodiimide for step (b) is dicyclohexylcarbodiimide.

Another embodiment of this invention is a composition made by a processof the invention, which may for example be a composition of theinvention. A composition comprising at least one compound of each of theFormulas (I), (II) and (III) may be obtained by

(a) providing one or more organic polyol(s) comprising at least twohydroxyl groups and at least two covalently bonded carbon atoms, eachhydroxyl group being bonded to a different carbon atom within an organicpolyol; and

(b) reacting the organic polyol(s), optionally in the presence of abase, with (i) one or more functionalized alkyl acid(s) or acidhalide(s) as represented by the structure of the following Formula (X):

Z-(CH₂)_(n)—C(O)X   (X)

wherein X is Cl, Br, I, or OH; Z is Br, I, —OTs, —OTf, or —OMs; and n isan integer equal to 3 to 20; and

-   (ii) one or more non-functionalized alkyl acid(s) or acid halide(s)    represented by the structure of the following Formula (XI):

Y—(CH₂)_(t)—C(O)X   (XI)

wherein X is Cl, Br, I, or OH; Y is H; and t is an integer equal to 3 to20; with the proviso that Z is not equal to Y; in a reaction solvent andat a reaction temperature to provide a mixture comprising thecomposition and a spent reaction mixture.

The compositions of the invention, such as those comprising at least onecompound of Formulas (VIIIa-VIIIe) and (IXa-IXe), are useful in liquidcrystal compositions, which are another embodiment of the invention.Many of these compositions exhibit nematic phases upon melting.Compositions of various embodiments of the invention are given below inthe examples with their corresponding thermal transitions that definetheir respective nematic phases.

In further embodiments of the invention, the liquid crystal compositionsmay include at least one chiral compound, including polymerizable and/ornon-polymerizable chiral monomers. A preferred liquid crystalcomposition comprises at least one compound of Formulas (VIIIa-VIIIe)and (IXa-IXe).

Chiral compounds, including cholesteryl esters or carbonates, such asbenzoate esters, alkyl esters and alkyl carbonates of cholesterol, areknown to exhibit cholesteric phases and are known to be useful ininducing chirality in a nematic phase to produce a twisted nematicphase. The terms “twisted nematic phase”, “cholesteric phase” and“chiral nematic” as used herein are synonymous. Cholesteryl estersuseful for incorporation into liquid crystal compositions of thisinvention include cholesteryl benzoate, cholesteryl 4-alkylbenzoates andcholesteryl 4-alkoxybenzoates wherein the alkyl and alkoxy groups are C₁to C₈ straight or branched chain alkyl groups, cholesteryl propionate,cholesteryl butanoate, cholesteryl hexanoate, cholesteryl octanoate,cholesteryl decanoate, cholesteryl undecantoate, cholesteryldodecanoate, cholesteryl hexadecanoate, and cholesteryl octadecanoate.Cholesteryl carbonates useful for this purpose include phenylcholesteryl carbonate, 4-alkylphenyl cholesteryl carbonates,4-alkoxyphenyl cholesteryl carbonates, and alkyl cholesteryl carbonateswherein the alkyl or alkoxy groups are C₁ to C₈ straight or branchedchain alkyl groups.

In one embodiment of a composition of this invention, the incorporatedchiral compounds are polymerizable chiral monomers and includepolymerizable cholesterol derivatives as described in U.S. Pat. No.4,637,896; polymerizable terpenoid derivatives as described in U.S. Pat.No. 6,010,643; polymerizable derivatives wherein the chiral center is anasymmetric carbon atom of a branched alkyl chain as described in U.S.Pat. No. 5,560,864; polymerizable derivatives of vicinal diols orsubstituted vicinal diols as described in U.S. Pat. No. 6,120,859 andU.S. Pat. No. 6,607,677; and polymerizable chiral compounds as describedin U.S. Pat. No. 6,723,395, U.S. Pat. No. 6,217,792, U.S. Pat. No.5,942,030, U.S. Pat. No. 5,885,242, and U.S. Pat. No. 5,780,629.Additional examples of suitable chiral compounds are described incopending and commonly owned published US-A-2007/0267599, WO2009/023759, and WO 2009/023762. The references listed above in thisparagraph are by this reference each incorporated in its entirety as apart hereof for all purposes.

A preferred group of polymerizable chiral monomers for use in thecompositions of this invention are those represented by the structure ofthe following Formula (XV):

wherein R¹ and R² are each independently selected from the group: H, F,Cl and CH₃; n1 and n2 are each independently integers 3 to 20; q and rare each independently integers 0, 1 or 2 with the proviso that q+r is≧1; D is a divalent chiral radical selected from the group:

and B³ and B⁴ are each divalent radicals independently selected from thegroup: R¹¹-substituted-1,4-phenyl, wherein R¹¹ is H, —CH₃ or —OCH₃;2,6-naphthyl; and 4,4′-biphenyl; provided that when q+r 3, at least oneof B³ and B⁴ is R⁴-substituted-1,4-phenyl; and when q+r 4, at least twoof B³ and B⁴ are R⁴-substituted-1,4-phenyl. Preferably R¹ and R² areindependently H, or CH₃; and n1 and n2 are independently an integer 3 to10.

Choices may be made from within and among the prescribed ranges for thevariable radicals and substituents such that the compound of Formula(XV) is, for example, either symmetric or asymmetric.

Another preferred group of polymerizable chiral monomers for practicingthis invention are those represented by the structure of the followingFormula (XVI):

wherein R¹ is selected from the group: H, F, Cl and CH₃; E is selectedfrom the group: —(CH₂)_(n7)—, —(CH₂)_(n8)O—, and —(CH₂CH₂O)_(n9)—; n7and n8 are each integers 3 to 20; n9 is an integer 1 to 4; and y is aninteger 0 or 1.

Forming a liquid crystal layer from a composition of this invention thatoptionally comprises a chiral monomer can be accomplished by any methodthat gives a uniform layer, or if desired, a patterned or non-uniformlayer. Coating, including rod-coating, extrusion coating, gravurecoating and spin-coating, spraying, printing, blading, knifing, or acombination of methods, can be used. Coating and knifing are preferredmethods. Many commercial coating machines, devices such as a coating rodand knife blade, and printing machines can be used to apply the liquidcrystal mixture as a liquid crystal or isotropic phase.

The ability of a twisted nematic phase to reflect light is dependentupon the alignment or texture of the twisted nematic phase. For manyapplications wherein a high degree of transparency is required outsidethe reflection band, or in applications that require very well definedreflection bands, a high degree of uniformity in a planar or homogeneousalignment is required. Discontinuities and domain boundaries in a planaralignment can cause a high degree of haze and degradation of thereflection band. A high degree of uniformity in planar alignment can beaccomplished with a combination of alignment layers and/or mechanicalshearing of the twisted nematic phase during and/or after application tothe substrate(s). Alignment layers typically are polymers that areapplied to substrates and mechanically buffed with a rubbing cloth oroptically aligned with polarized light. The buffing or optical alignmentallows the liquid crystal molecules applied to the interface to align inone direction. Useful polyimide alignment layers, for example, aredescribed in U.S. Pat. No. 6,887,455. Alignment of twisted nematicphases by coating of dilute liquid crystal mixtures is described in U.S.Pat. No. 6,410,130.

Treating the liquid crystal layer to provide a desired liquid crystalphase can include steps such as cooling or heating the liquid crystallayer, for instance to achieve a desired phase or optical property;application of a mechanical shear to the liquid crystal layer, forinstance by application of a knife blade to the liquid crystal layer orshearing two or more substrates wherein the liquid crystal layer isinterposed; or vibration, sonication or other form of agitation to thesubstrate(s).

Liquid crystal compositions as provided by this invention may furthercomprise small amounts of a polymerizable diluent that may include, forexample, 2-ethoxyethyl acrylate, diethylene glycol diacrylate, ethyleneglycol dimethacrylate, diethylene glycol dimethacrylate, triethyleneglycol dimethacrylate, diethylene glycol monomethyl ether acrylate,phenoxyethyl acrylate, tetraethylene glycol dimethacrylate,pentaerythritol tetraacrylate and ethoxylated pentaerythritoltetraacrylate.

Liquid crystal compositions as provided by this invention may furthercomprise small amounts of typical additives such as one or more ofsurfactants, leveling agents, viscosity modifiers, wetting agents,defoamers and UV stabilizers. Selection will often be based uponobserved coating and alignment quality and the desired adhesion of theliquid crystal coating to the substrate and other layers. Typicalsurfactants comprise siloxy-, fluoryl-, alkyl-and alkynyl-substitutedsurfactants. These include the Byk® (Byk Chemie), Zonyl® (DuPont),Triton® (Dow), Surfynol® (Air Products) and Dynol® (Air Products)surfactants.

The ability of twisted nematic phases to selectively reflect light inthe infrared, visible or ultraviolet region is useful in manyapplications. When the propagation direction of plane polarized orunpolarized light is along the helical axis of the twisted nematiclayer, the wavelength of maximum reflection, λ₀, is governed by theequation λ₀=n_(a) p, wherein n_(a) is the average of n_(o) and n_(e),and n_(o) and n_(e) are defined as the ordinary and extraordinaryrefractive indices respectively, of the twisted nematic phase measuredin the propagation direction and p is the pitch of the helix (thedistance the helix takes to repeat itself). Light outside the vicinityof λ₀ is essentially unaffected in transmission. For light with awavelength in the vicinity of wavelength λ₀, the twisted nematic phaseexhibits selective reflection of the light such that approximately 50%of the light is reflected and approximately 50% of the light istransmitted, with both the reflected and transmitted beams beingsubstantially circularly polarized. A right handed helix reflects righthanded circularly polarized light and transmits left handed circularlypolarized light. The bandwidth Δλ of this reflected wavelength bandcentered about λ₀ can be determined by the formula Δλ=λ₀·Δn/n_(a), whereΔn=n_(e)−n_(o), reflecting the birefringence present in liquid crystalmaterials. The pitch p can be tuned effectively by manipulating theamount of chiral dopant, the twisting power of the dopant and selectionof the nematic materials. The pitch is sensitive to temperature,unwinding or tightening with a change in temperature; and to electricfields, dopants, and other environmental considerations. Thus, in thetwisted nematic phase, manipulation of the pitch, and thus thewavelength of maximum reflection, can be accomplished with a widevariety of tools. Furthermore, the bandwidth Δλ of the reflectedwavelength band also can be manipulated in the manner described in U.S.Pat. No. 5,506,704 and U.S. Pat. No. 5,793,456.

Articles derived from a composition of the invention are useful asoptical elements or components of an optical element. An optical elementis any film, coating or shaped object that is used to modify thecharacteristics of light. The modifications produced by optical elementsinclude changes in the intensity of light through changes intransmission or reflectivity, changes in wavelength or wavelengthdistribution, changes in the state of polarization, changes in thedirection of propagation of part or all of the light, or changes in thespatial distribution of intensity by, for example, focusing,collimating, or diffusing the light. Examples of optical elementsinclude linear polarizers, circular polarizers, lenses, mirrors,collimators, diffusers, reflectors and the like. Examples of theusefulness of articles, including optical elements, comprising liquidcrystal compositions are provided, for example, in a general review byP. Palffy-Muhoray in “The Diverse World of Liquid Crystals”, PhysicsToday (2007), 60(9), pp. 54-60.

EXAMPLES

The advantageous attributes and effects of this invention may be morefully appreciated from a series of examples (Examples 1˜3), as describedbelow. The embodiments on which the examples are based arerepresentative only, however, and the selection of those embodiments toillustrate the invention does not indicate that materials, conditions,specifications, components, regimes, reactants, steps, ingredients, ortechniques not described in these examples are not suitable forpracticing this invention, or that subject matter not described in theseexamples is excluded from the scope of the appended claims andequivalents thereof.

In the following examples, thermal transitions are given in degreesCentigrade. The following notations are used to describe the observedphases: K=crystal, N=nematic, S=smectic, TN*=twisted nematic,X=unidentified phase, I=isotropic, P=polymerized. The thermaltransitions and phase assignments were made with differential scanningcalorimetry and hotstage optical microscopy. Unless noted otherwise, thephase behavior refers to the first heating cycle.

Compound 1 was obtained as described in US-A-2007/0228326. All othermaterials used in the examples were obtained from commercial sources.

Example 1

This example illustrates the formation of Mixture 1, a liquid crystalmixture of one embodiment of the invention. Mixture 1 corresponds to acomposition comprising one compound of Formula (I), two compounds ofFormula (II), and one compound of Formula (III).

10 g of Compound 1 was dissolved in 40 mL THF and 9.5 mL triethylamineand cooled to 0° C. A mixture of 8.96 g 6-bromohexanoyl chloride and1.68 g valeroyl chloride in 60 mL THF was added dropwise over 20minutes. Stirring was continued for another 30 minutes at 0° C. Thecooling bath was removed and the reaction allowed to stir for anadditional 90 minutes. The reaction was filtered to remove salts and thesalts were washed with THF. Approximately 75% of the solvent was removedunder reduced pressure and the crude oil was added to an excess ofwater, forming a colorless precipitate. The solids were filtered, washedwith water, methanol, and dried to provide 17.74 g of Mixture 1. 1^(st)heating: K 81-85 N 177-179 I

Example 2

This example illustrates the formation of Mixture 2, a liquid crystalmixture of one embodiment of the invention. Mixture 2 corresponds to acomposition comprising one compound of Formula (I), four compounds ofFormula (II), and four compounds of Formula (III).

10 g of Compound 1 was dissolved in 40 mL THF and 9.5 mL triethylamineand the solution was cooled to 0° C. A mixture of 9.56 g 6-bromohexanoylchloride, 0.75 g hexanoyl chloride, and 0.91 g octanoyl chloride in 30mL THF was added dropwise over 20 minutes. The reaction mixture wasstirred for another 30 minutes at 0° C., the cooling bath was removedand the reaction was allowed to stir for an additional 90 minutes. Thereaction mixture was filtered to remove salts, the salts were rinsedwith THF and the organics were diluted with diethyl ether and washedwith water. The organics were dried over MgSO₄, filtered, andconcentrated to provide 18.58 g of Mixture 2 as an off-white solid.1^(st) heating: K 85-91 N 166-171 I

Example 3

This example illustrates the formation of Mixture 3, a liquid crystalmixture of one embodiment of the invention. Mixture 3 corresponds to acomposition comprising four compounds of Formula (I), eight compounds ofFormula (II), and four compounds of Formula (III).

TABLE 2 Statistical Mixture of Compounds with Average Molecular Weightof 678.4535 g/mol in Mixture 3 Isomer Mole % a Z b Y 1 30.25 5 Br 5 Br 213.75 5 Br 3 Br 3 5.50 5 Br 5 H 4 5.50 5 Br 7 H 5 13.75 3 Br 5 Br 6 6.253 Br 3 Br 7 2.50 3 Br 5 H 8 2.50 3 Br 7 H 9 5.50 5 H 5 Br 10 2.50 5 H 3Br 11 1.00 5 H 5 H 12 1.00 5 H 7 H 13 5.50 7 H 5 Br 14 2.50 7 H 3 Br 151.00 7 H 5 H 16 1.00 7 H 7 H

Each of the formulae shown herein describes each and all of theseparate, individual compounds that can be formed in that formula by (i)selection from within the prescribed range for one of the variable,substituents or numerical coefficients while all of the other variableradicals, substituents or numerical coefficients are held constant, and(ii) performing in turn the same selection from within the prescribedrange for each of the other variable radicals, substituents or numericalcoefficients with the others being held constant. In addition to aselection made within the prescribed range for any of the variableradicals, substituents or numerical coefficients of only one of themembers of the group described by the range, a plurality of compoundsmay be described by selecting more than one but less than all of themembers of the group of radicals, substituents or numericalcoefficients. When the selection made within the prescribed range forany of the variable radicals, substituents or numerical coefficients isa subgroup containing (a) only one of the members of the group describedby the range, or (b) more than one but less than all of the members ofthe group, the selected member(s) are selected by omitting thosemember(s) of the whole group that are not selected to form the subgroup.The compound, or plurality of compounds, may in such event be describedas containing one or more variable radicals, substituents or numericalcoefficients each of which variable radicals, substituents or numericalcoefficients is defined by the members of the whole group, described bythe range for that variable radical, substituent or numericalcoefficient in the absence of the member(s) omitted to form thesubgroup.

Certain features of this invention are described herein in the contextof an embodiment that combines various such features together, whetheras described in the disclosure or in one of the drawings. The scope ofthe invention is not, however, limited by the description of onlycertain features within any particular embodiment, and the inventionalso includes (1) a subcombination of fewer than all of the features ofany described embodiment, which subcombination is characterized by theabsence of the features omitted to form the subcombination; (2) each ofthe features, individually, included within the combination of thedescribed embodiment; and (3) other combinations of features formed fromone or more or all of the features of the described embodiment togetherwith other features as disclosed elsewhere herein.

Where a range of numerical values is recited herein, the range includesthe endpoints thereof and all the individual integers and fractionswithin the range, and also includes each of the narrower ranges thereinformed by all the various possible combinations of those endpoints andinternal integers and fractions to form subgroups of the larger group ofvalues to the same extent as if each of those narrower ranges wasexplicitly recited. Where a range of numerical values is stated hereinas being greater than a stated value, the range is nevertheless finiteand is bounded on its upper end by a value that is operable within thecontext of the invention as described herein. Where a range of numericalvalues is stated herein as being less than a stated value, the range isnevertheless bounded on its lower end by a non-zero value.

In this specification, unless explicitly stated otherwise or indicatedto the contrary by the context of usage, where an embodiment of thisinvention is stated or described as comprising, including, containing,having, being composed of or being constituted by or of certain featuresor elements, one or more features or elements in addition to thoseexplicitly stated or described may be present in the embodiment. Analternative embodiment of this invention, however, may be stated ordescribed as consisting essentially of certain features or elements, inwhich embodiment features or elements that would materially alter theprinciple of operation or the distinguishing characteristics of theembodiment are not present therein. A further alternative embodiment ofthis invention may be stated or described as consisting of certainfeatures or elements, in which embodiment, or in insubstantialvariations thereof, only the features or elements specifically stated ordescribed are present.

In this specification, unless explicitly stated otherwise or indicatedto the contrary by the context of usage,

(a) amounts, sizes, formulations, parameters, and other quantities andcharacteristics recited herein, particularly when modified by the term“about”, may but need not be exact, and may be approximate and/or largeror smaller than stated (as desired), reflecting tolerances, conversionfactors, rounding off, measurement error and the like, as well as theinclusion within a stated value of those values outside it that have,within the context of this invention, functional and/or operableequivalence to the stated value;

(b) all numerical quantities of parts, percentage or ratio are given asparts, percentage or ratio by weight;

(c) use of the indefinite article “a” or “an” with respect to astatement or description of the presence of an element or feature ofthis invention, does not limit the presence of the element or feature toone in number;

(d) the words “include”, “includes” and “including” are to be read andinterpreted as if they were followed by the phrase “without limitation”if in fact that is not the case; and

(e) the word “or”, as used herein, is inclusive; more specifically, thephrase “A or B” means “A, B, or both A and B”; and use of “or” in anexclusive sense is designated, for example, by terms such as “either Aor B” and “one of A or B”.

1. A process for making a composition comprising: (a) providing one ormore organic polyol(s) comprising at least two hydroxyl groups and atleast two covalently bonded carbon atoms, each hydroxyl group beingbonded to a different carbon atom within an organic polyol; (b) reactingthe organic polyol(s), optionally in the presence of a base, with (i)one or more functionalized alkyl acid(s) or acid halide(s) representedby the structure of the following Formula (X):Z-(CH₂)_(n)—C(O)X   (X) wherein X is Cl, Br, I, or OH; Z is F, Cl, Br,I, —OTs, —OTf, —OMs, CN, or NO₂; and n is an integer equal to 3 to 20;and (ii) one or more non-functionalized alkyl acid(s) or acid halide(s)represented by the structure of the following Formula (XI):Y—(CH₂)_(t)—C(O)X   (XI) wherein X is Cl, Br, I, or OH; Y is H, F, Cl,Br, I, —OTs, —OTf, —OMs, CN, or NO₂; and t is an integer equal to 3 to20; with the proviso that Z is not equal to Y; in a reaction solvent andat a reaction temperature to provide a mixture comprising a compositionand a spent reaction mixture.
 2. The process of claim 1 wherein thepolyol comprises a diol selected from the group of compounds representedby the structures of the following Formulas (XIIIa-XIIIg):

wherein R³-R¹⁰ are selected from the group: H, C₁-C₈ straight orbranched chain alkyl, C₁-C₈ straight or branched chain alkyloxy, F, Cl,phenyl, —C(O)CH₃, CN and CF₃; and R¹¹ is H, —CH₃ or —OCH₃.
 3. Theprocess of claim 1 wherein the polyol comprises a diester diol selectedfrom the group of materials represented by the structures of thefollowing Formulas (XIVa-XIVf):

wherein R³-R¹⁰ are selected from the group: H, C₁-C₈ straight orbranched chain alkyl, C₁-C₈ straight or branched chain alkyloxy, F, Cl,phenyl, —C(O)CH₃, CN and CF₃; and R¹¹ is H, —CH₃ or —OCH₃.
 4. Acomposition as prepared according to the process of claim 1.